CN109475814A - Use of urea composition to produce diesel exhaust fluid (AUS 32) - Google Patents
Use of urea composition to produce diesel exhaust fluid (AUS 32) Download PDFInfo
- Publication number
- CN109475814A CN109475814A CN201780043369.2A CN201780043369A CN109475814A CN 109475814 A CN109475814 A CN 109475814A CN 201780043369 A CN201780043369 A CN 201780043369A CN 109475814 A CN109475814 A CN 109475814A
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- Prior art keywords
- component
- weight
- dalton
- urea
- particulate composition
- Prior art date
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000004202 carbamide Substances 0.000 title claims abstract description 108
- 239000000203 mixture Substances 0.000 title claims abstract description 91
- 239000012530 fluid Substances 0.000 title claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims description 35
- 229920002873 Polyethylenimine Polymers 0.000 claims description 29
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 21
- 150000008065 acid anhydrides Chemical class 0.000 claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract 1
- 235000013877 carbamide Nutrition 0.000 description 100
- 239000000243 solution Substances 0.000 description 58
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 45
- 239000002245 particle Substances 0.000 description 29
- 239000000428 dust Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 239000013590 bulk material Substances 0.000 description 12
- 238000005469 granulation Methods 0.000 description 10
- 230000003179 granulation Effects 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003337 fertilizer Substances 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 7
- 229920001807 Urea-formaldehyde Polymers 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003981 vehicle Substances 0.000 description 4
- WVOXLKUUVCCCSU-ZPFDUUQYSA-N Pro-Glu-Ile Chemical compound [H]N1CCC[C@H]1C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H]([C@@H](C)CC)C(O)=O WVOXLKUUVCCCSU-ZPFDUUQYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000000412 dendrimer Substances 0.000 description 3
- 229920000736 dendritic polymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 description 2
- XXJGBENTLXFVFI-UHFFFAOYSA-N 1-amino-methylene Chemical compound N[CH2] XXJGBENTLXFVFI-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PWLXTFFHCFWCGG-UHFFFAOYSA-N Heneicosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCC(O)=O PWLXTFFHCFWCGG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000333 poly(propyleneimine) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005588 protonation Effects 0.000 description 2
- 239000011802 pulverized particle Substances 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 description 1
- 229920003656 Daiamid® Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 238000005574 benzylation reaction Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- INDBQLZJXZLFIT-UHFFFAOYSA-N primaquine Chemical compound N1=CC=CC2=CC(OC)=CC(NC(C)CCCN)=C21 INDBQLZJXZLFIT-UHFFFAOYSA-N 0.000 description 1
- 229960005179 primaquine Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
- C05C9/005—Post-treatment
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2066—Selective catalytic reduction [SCR]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2067—Urea
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/08—Preparation of ammonia from nitrogenous organic substances
- C01C1/086—Preparation of ammonia from nitrogenous organic substances from urea
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/18—Nitrates of ammonium
- C01C1/185—Preparation
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2610/00—Adding substances to exhaust gases
- F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Toxicology (AREA)
- Fertilizers (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
- Treating Waste Gases (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及用于生产NOx还原剂AUS 32溶液(柴油机排气处理液)的方法，所述方法包括至少将水和颗粒组合物混合，所述颗粒组合物包含：(i)脲；和包含组分(ii)的添加剂：(ii)至少一种包含氨基的聚合物或低聚物与至少一种官能化聚乙烯基化合物的组合；其中所述颗粒组合物中组分(i)的重量百分比大于60重量％，所述颗粒组合物中组分(ii)的重量百分比小于1重量％，其中获得脲溶液，并且所获得的脲溶液中组分(i)的重量百分比为31重量％至34重量％。The present invention relates to a method for producing a NOx reducing agent AUS 32 solution (diesel exhaust fluid), the method comprising mixing at least water and a particulate composition comprising: (i) urea; and comprising Additives to component (ii): (ii) a combination of at least one amino group-containing polymer or oligomer and at least one functionalized polyvinyl compound; wherein the weight of component (i) in the particulate composition The percentage is greater than 60% by weight, the percentage by weight of component (ii) in the granular composition is less than 1% by weight, wherein a urea solution is obtained, and the percentage by weight of component (i) in the obtained urea solution is 31% by weight to 34% by weight.
Description
The present invention relates to produce NO containing urea compositions by particlex32 solution (diesel exhaust fluid of reducing agent AUS
(disel exhaust fluid)) method, its purposes in diesel-engine road vehicle and can obtain by means of the present invention
NOx32 solution of reducing agent AUS (diesel exhaust fluid).
It is known in the state of the art a variety of for producing method of the particle containing urea compositions.In the past, urea particle, which is generally as follows, to be come
Production: by means of spray crystallization, by ambient temperature will substantially anhydrous urea melt (water content be 0.1 weight % extremely
0.3 weight %) it is sprayed onto ascending air stream from the top of spray crystallization tower, and solidify drop to obtain crystal (particle).
Thus obtained particle has relatively small diameter and low mechanical strength.
Currently, the urea particle with greater particle size and preferable mechanical property usually passes through in a fluidized bed to substantially anhydrous
Urea melt or aqueous urea solution pelletize to produce, such as such as US 4, described in 219,589.In these pelletizations
In, it with average diameter is 20 μm to 120 μm very thin by aqueous urea solution that urea concentration is 70 weight % to 99.9 weight %
The form of the drop of dispersion is introduced into the fluidized bed of urea particle, and temperature is selected to make the water in the solution being sprayed on urea particle
It evaporates and is deposited on urea on particle, obtain the bulk material of the expectation particle size with 2.5mm or bigger.
Due to obtaining relatively great amount of fine dust in the method, especially when the water content of used urea solution is big
When 5 weight %, so the granule additive formed usually using this dust is reduced.The effect for adding these additives is grain
Shape particle and especially its surface keeps plasticity, so that being obtained due to its rolling movement and collision has smooth surface and good
The circular granular of mechanical stability.Therefore, thus obtained bulk material have high compression strength and impact resistance, it is low because
The tendency of dust is worn and formed, and furthermore there was only low caking tendency during long term storage.However, hair
Now corresponding granule additive is applied not only to fluidized bed granulation, but also is used for other methods, such as spray crystallization or rotary drum system
Grain.
Used granule additive is usually the water-soluble addition object and/or condensation product of formaldehyde or formaldehyde and urea,
But these must be added with relatively large amount, and due to its toxicity characteristic and in terms of processing not no problem.Formaldehyde leakage pair
Health and environment constitute serious risk, although introduce urea-formaldehyde prepolymer (such as UF80 or UF85) reduced it is such
Risk.In addition, according to IARC (international cancer research institution of a part as WHO, International Agency
For Research on Cancer) " carcinogen " classification, asked to the relevant health risk of formaldehyde vapors is exposed to for a long time
Topic also occurs, even if this can not be avoided completely by using such prepolymer.
Another problem in the granulation of urea is to form dust, and the dust is understood to imply diameter less than 0.5mm's
Particle.Dust is formed substantially due to three sources.First it should be mentioned that due to for example in a fluidized bed between particle
Movement and collision and caused by bulk material abrasion, wherein the amount of dust obtained is substantially dependent on the machine of bulk material
Tool characteristic.In addition, nozzle respectively generates the drop with certain diameter distribution, in this case, most thin drop is in its chance
Solidify before to urea particle, therefore the dust being consequently formed leaves granulator together with exhaust gas again.Finally, it should be mentioned that third
Source is the dust obtained by crushing excessive granular solid matter, is led in method and apparatus according to prior art (plant)
It is often transferred directly and returns in granulator.10 weight % to 20 weight % through pulverized particles have the diameter less than 1mm, and
Its high proportion is dust.Therefore, in final products per ton 1% to 1.5% dust returning through pulverized particles by the ratio
To granulator, and the 3% to 5% of total dust of the final products per ton from industrial equipment is attributed to granulator.
In order to avoid or reduce disadvantages mentioned above, have studied formaldehyde different substitutes and its water-soluble addition and/or
Condensation product, but every kind of substitute is also restrained or the influence of disadvantage.
As an example, using alkali metal lignosulfonates described in 766,302 with reference to such as US 5, or use second two
Aldehyde or carbohydrate.However, according to production method, these lead to faint yellow or brown in urea product obtained, this
It is in many cases (such as in the production of melamine) undesirable.On the other hand, (such as poly- using surface reactive material
The mixture of vinyl acetate and polyvinyl alcohol) it is used as granule additive to also result in problem, the reason is that these have blistering
Tendency, for example, when additive and melt mixed or in the washers when, wherein processed urea dust dissolves and damages washer
Efficiency.These substances formed foam tendency also final products are had an impact, final products have lower density and
It is not acceptable to the market.Therefore, generally speaking, the formation of foam tendency on the industrial application of urea granula is unacceptable.
In view of in relation to the nitrogen oxides (NO from diesel-engine road vehicleX) discharge tightened up environmental legislation, use work
The urea solution of industry grade purity becomes more and more important.Here urea solution is introduced into exhaust, and at selective catalytic reduction (SCR)
In the conversion of nitrogen oxides that be present in exhaust be nitrogen (N2) and water (H2O).Urea in injection exhaust is thermal decomposited ammonification
(NH3).Thus the ammonia discharged reduces the nitrogen oxides being present in exhaust.The urea solution of the technical grade purity is (also referred to as
Diesel exhaust fluid, AUS 32 (aqueous urea solution) or) composition it is very accurate according to ISO 22241
Ground regulation.The urea solution of technical grade purity includes the urea of 32.5 weight %.The list of qualitative characteristics and impurity can also see DIN
7007:2005-08.The limit of the standard special provision aldehyde is 5mg/kg.
Due to the strict regulations in relation to urea purity, it is impossible to use any desired urea source.It therefore, in general, will preparation
In the urea that directly obtains mixed and transported to place to use with determining concentration with softened water (distilled water).In this way, it removes
Except urea, up to 2/3 water is also transported.In addition, these aqueous solutions can not be transported and be stored for a long time as needed；On the contrary,
Biological decomposition may occur.Alternative solution (that is, granular urea is transported to place to use) is typically due to present in bulk material
Aldehyde and fail, which hinders be used as NOx32 solution of reducing agent AUS.
Therefore, it is an object of the present invention to provide contain urea compositions and aquatic production NO by particlexReducing agent AUS 32 is molten
The method of liquid (diesel exhaust fluid), if the shortcomings that this method makes the prior art at least becomes reduction using this method
Form.
The purpose is realized by the theme of specification and claims.
It was unexpectedly found that by means of the present invention, in the case where not using formaldehyde and urea-formaldehyde condensation product,
By by water with containing the mixing of urea, can obtain the particulate composition with desirable characteristics, and the particulate composition can be with
It is used together with softened water to produce NOx32 solution of reducing agent AUS (diesel exhaust fluid), advantageously according to ISO
22241.More particularly, in this way,
The particle containing urea met for producing the pureness specifications of 32 solution of AUS (diesel exhaust fluid) can be provided.
In addition, the production of 32 solution of AUS (diesel exhaust fluid) can be synthesized with urea and be separated, therefore amount to be transported can subtract
Few up to 2/3.This not only lowers necessary fuel consumptions, and also reduce the emission discharged in transportational process.In addition,
It is related to NOxThe cost of the packaging of 32 solution of reducing agent AUS and inconvenience significantly reduce.With for packing and transport less amount of grain
Shape urea is compared, and being related to will be in up to 2/3 NO of urea synthesis place weightx32 solution transportation and packaging of reducing agent AUS is extremely using ground
The cost and inconvenience of point are much higher；
Can to avoid with use formaldehyde and urea-formaldehyde condensation product it is related health and environmental risk；And/or
Compared with the composition for using formaldehyde and urea-formaldehyde condensation product to produce, can provide the cost of production composition compared with
Low alternative solution.Urea compositions of the invention allow using the granular urea optimized for fertilizer field.Of the invention is water-soluble
Urea compositions in liquid unexpectedly meet in the table 1 in standard DIN 70070:2005-08 to 32 solution (diesel engine of AUS
Gas exhaust treatment liquid) as defined in limitation.In contrast, the standard can not usually be met for the conventional urea compositions of fertilizer field,
Especially because high content of formaldehyde；And/or
It can be reduced or even completely avoided and form dust during the production of composition, and/or
Such particulate composition can be obtained: compared with the composition for using formaldehyde and urea-formaldehyde condensation product to produce,
Particle shows at least comparable or even preferably characteristic, especially for mechanical property, for example, compression strength, shock resistance
Property, low abrasion or caking tendency, especially in prolonged storage.
The present invention relates to for producing NOxThe method of 32 solution of reducing agent AUS (diesel exhaust fluid), the side
Method includes at least mixing water and particulate composition, and the particulate composition includes:
(i) urea；
With the additive comprising component (ii):
(ii) the amino-containing polymer of at least one packet or oligomer and at least one functional polyethylene based compound
Combination；
Wherein the ratio by mass of component (i) is calculated as > 60 weight % in the particulate composition, in the particulate composition
The ratio by mass of component (ii) is calculated as < 1 weight %, and
Urea solution is wherein obtained, and the ratio by mass of component (i) is calculated as 30 weight % extremely in urea solution obtained
35 weight % (including endpoint value), especially 31 weight % are to 34 weight %, especially 31.8 weight % to 33.2 weight %.Institute
Urea solution of the concentration range of acquisition within the concentration range as defined in ISO 22241 corresponds to NOx32 solution of reducing agent AUS
(diesel exhaust fluid).
Particulate composition of the invention preferably include only a small amount of (if any) less than 20ppm aldehyde and/or
Sulphur.In the context of the present invention, it means that obtainable NOxThe component mentioned in 32 solution of reducing agent AUS is to be lower than
Concentration as defined in ISO 22241 and/or DIN 70070:2005-08 exists.
The amino-containing polymer of packet used according to the invention and oligomer particularly include having following molecular weight (MW)
Polymer and oligomer: 250 dalton to 2000000 dalton, 300 dalton to 2000000 dalton, 350 dalton
To 2000000 dalton, 400 dalton to 2000000 dalton, 450 dalton to 2000000 dalton, 500 dalton
To 2000000 dalton, 550 dalton to 2000000 dalton, 600 dalton to 2000000 dalton, 650 dalton
Extremely to 2000000 dalton, 700 dalton to 2000000 dalton, 750 dalton to 2000000 dalton, 800 dalton
2000000 dalton, 850 dalton to 2000000 dalton, 900 dalton to 2000000 dalton, 950 dalton are extremely
2000000 dalton, 1000 dalton to 2000000 dalton, 1050 dalton to 2000000 dalton, 1100 dalton
To 2000000 dalton, 1150 dalton to 2000000 and 1200 dalton to 2000000 dalton.
For example, the molecular weight (MW) of the amino-containing polymer of used according to the invention packet and oligomer can be with are as follows: 500
Dalton is to 1000000 dalton, 550 dalton to 1000000 dalton, 600 dalton to 1000000 dalton, 650
Dalton is to 1000000 dalton, 700 dalton to 1000000 dalton, 750 dalton to 1000000 dalton, 800
Er Dun is to 1000000 dalton, 850 dalton to 1000000 dalton, 900 dalton to 1000000 dalton, 950
Er Dun is to 1000000 dalton, 1000 dalton to 1000000 dalton, 1050 dalton to 1000000 dalton, 1100
Dalton is to 1000000 dalton, 1150 dalton to 1000000 and 1200 dalton to 1000000 dalton, Huo Zheke
In following range: 500 dalton to 10000 dalton, 550 dalton to 10000 dalton, 600 dalton are extremely
10000 dalton, 650 dalton to 10000 dalton, 700 dalton to 10000 dalton, 750 dalton to 10000
Dalton, 800 dalton to 10000 dalton, 850 dalton to 10000 dalton, 900 dalton to 10000 dalton,
950 dalton to 10000 dalton, 1000 dalton to 10000 dalton, 1050 dalton to 10000 dalton, 1100
Dalton is to 10000 dalton, 1150 dalton to 10000 and 1200 dalton to 10000 dalton.
Preferably, it wraps amino-containing polymer and oligomer can have the weight based on polymer or oligomer as 10 weights
The nitrogen content of % to 50 weight % is measured, and includes primaquine, parahelium or tertiary amino group, the group independently includes alkyl or virtue
Base alkyl, such as C1-6Alkyl or aryl-C1-3Alkyl, wherein aryl particularly can be phenyl or pyridyl group, can be without
Replace or optionally through independently selected from F, Cl, Br, CF3、C1-6Alkyl, C1-6Alkoxy, NH2、C1-6Alkyl amino and two (C1-6
Alkyl) 1,2,3,4 or 5 substituent group in amino replaces.
For example, the amino-containing polymer of available packet and oligomer include that the vinyl that replaces of polyamines, polymerized polyamines, nitrogen is poly-
It closes object, gatherOxazoline, polypropyleneimine and its dendrimers, polyethyleneimine and its dendrimers, daiamid and its
The copolymer of two or more and derivative and combination in dendrimers and mentioned substance.
It preferably wraps amino-containing polymer and oligomer includes that polyamines and polymerized polyamines, polyalkyleneimine are (such as poly-
Aziridine and polypropyleneimine), polyvinylamine, poly-alkoxylation polyamines, ethoxylated polyamine, propoxylation polyamines, alkyl
Change and the combination of two or more in Benzylation polyamines and aforementioned component.
The amino-containing polymer of the packet particularly preferably used and oligomer are polyethyleneimine, the tree-shaped polymerization of polyethyleneimine
At least two mixture in object and its copolymer, derivative and these components.
Suitable polyethyleneimine may include the poly- second of linear or branching with such as 10 or more monomeric units
At least two mixing in alkene imine polymer or oligomer and its derivative, analog, copolymer and these components
Object.
Polyethyleneimine can be obtained by the polymerization of aziridine and can be on the market with for exampleWithThe form of product family is commercially available, is especially hereinG20、FG、
G35、P and1595 products (Product available from BASF (Florham Park, NJ,
USA)), andSP-003、SP-006、 SP-
018、SP-200、SP-1000 andSP-1050(Product available from
Nippon Shokubai(Osaka,Japan))。
According to the present invention, available functional polyethylene based compound particularly includes based on repetition (CHXCHY)nUnit
Compound, wherein X be selected from H, NH2、OH、COOH、COR、 CONH2、CH2NH2、CH2NHR、CH2OH and CH2OR, and Y is selected from
NH2、OH、 COOH、COR、CONH2、CH2NH2、CH2NHR、CH2OH and CH2OR, and wherein R independently is in each case
Alkyl, especially C1-6Alkyl or aryl, especially phenyl or pyridyl group can be unsubstituted or optionally independently be selected
From F, Cl, Br, CF3、C1-6Alkyl, C1-6Alkoxy, NH2、C1-6Alkyl amino and two (C1-6Alkyl) in amino 1,2,3,4 or
5 substituent groups replace.
For example, the molecular weight (MW) of functional polyethylene based compound used according to the invention can be with are as follows: 250 dalton
To 2000000 dalton, 300 dalton to 2000000 dalton, 350 dalton to 2000000 dalton, 400 dalton
To 2000000 dalton, 450 dalton to 2000000 dalton, 500 dalton to 2000000 dalton, 550 dalton
To 2000000 dalton, 600 dalton to 2000000 dalton, 650 dalton to 2000000 dalton, 700 dalton
Extremely to 2000000 dalton, 750 dalton to 2000000 dalton, 800 dalton to 2000000 dalton, 850 dalton
2000000 dalton, 900 dalton to 2000000 dalton, 950 dalton to 2000000 dalton, 1000 dalton are extremely
2000000 dalton, 1050 dalton to 2000000 dalton, 1100 dalton to 2000000 dalton, 1150 dalton
To 2000000 dalton and 1200 dalton to 2000000 dalton.
Available functional polyethylene based compound preferably includes or mixtures thereof polyvinyl alcohol or polyvinylamine.Function
Change polyvinyl compound and is more preferably polyvinylamine.
Polyvinylamine and the respective molecular weight of polyvinyl alcohol (MW) can advantageously be: 500 dalton to 1000000 dongles
Pause, 550 dalton to 1000000 dalton, 600 dalton to 1000000 dalton, 650 dalton to 1000000 dongles
Pause, 700 dalton to 1000000 dalton, 750 dalton to 1000000 dalton, 800 dalton to 1000000 dongles
Pause, 850 dalton to 1000000 dalton, 900 dalton to 1000000 dalton, 950 dalton to 1000000 dongles
Pause, 1000 dalton to 1000000 dalton, 1050 dalton to 1000000 dalton, 1100 dalton to 1000000
Er Dun, 1150 dalton to 1000000 and 1200 dalton are to 1000000 dalton, or in following range: 500 dongles
Pause to 10000 dalton, 550 dalton to 10000 dalton, 600 dalton to 10000 dalton, 650 dalton extremely
10000 dalton, 700 dalton to 10000 dalton, 750 dalton to 10000 dalton, 800 dalton to 10000
Dalton, 850 dalton to 10000 dalton, 900 dalton to 10000 dalton, 950 dalton to 10000 dalton,
1000 dalton to 10000 dalton, 1050 dalton to 10000 dalton, 1100 dalton to 10000 dalton, 1150
Dalton is to 10000 and 1200 dalton to 10000 dalton.
Suitable polyvinylamine particularly includes the linear polymer and copolymer of derived from ethylene base formyl amine monomers, and
And it may include cation and anion polyvinylamine copolymer and electrification and protonation polyvinylamine.
Suitable polyvinylamine be can on the market it is commercially available for example fromThose of product family, and
And it is especially herein1595、4500、5095、9030、9050 Hes9095 products.The example of cation and anion polyvinylamine copolymer is to come fromThose of product family, and be especially hereinAm na、AV、
VH、VI、VM、PR8094、PR8261 and
PR8349 product.The example of electrification or protonation polyvinylamine is to come fromThe product of product line, and
It is especially product hereinGM、PL、PR8236、VCB、VFH、VLW、VMP andVSH。WithProduct is available from BASF (Florham Park, NJ, USA).
Unless otherwise stated, the weight figure (weight %) given in conjunction with particulate composition is in each case always
It is related to the total weight of particulate composition.It would be recognized by those skilled in the art that given component and weight figure does not need to meet
Any arbitrarily small part of particle, but meet the average value of the representative amount of produced particle.
Unless otherwise stated, in conjunction with NOxWeight figure (the weight that 32 solution of reducing agent AUS or urea solution give
Amount %) always it is related to NO in each casexThe total weight of 32 solution of reducing agent AUS or urea solution.
Particulate composition of the invention can optionally include other compositions and mentioned ingredient.The property of ingredient and
Its amount depends on for example used component (i).For example, particulate composition of the invention may include: such as 0.05 weight %
The water of amount to 0.5 weight %, particularly 0.1 weight % to 0.3 weight %, and the by-product such as biuret from urea synthesis
Or NH3.In general, the ratio of by-product is not more than 1.5 weight %, especially not greater than 1.25 weight %.
In a preferred embodiment of the method, particulate composition includes at least one compound selected from the following
As additive component (iii): aliphatic dicarboxylic acid, its salt and acid anhydrides, aliphatic tricarboxylic acids, its acid anhydrides, aromatic dicarboxylic acid, its salt and
Acid anhydrides and acid anhydrides, wherein preferably, the ratio by mass of component (i) is calculated as in > 60 weight % and the composition
The ratio by mass of the summation of component (ii) and component (iii) is calculated as < 1 weight %.
It will be apparent to one skilled in the art that component (ii) and component for producing particulate composition
(iii) it can partially or even wholly may interact with another one and be also possible to interact with urea component (i).Example
Such as, it is known that aldehyde or carboxylic acid anhydrides and urea are cross-linked to form covalent bond, or form the complex of urea and carboxylic acid.Such as polyvinyl alcohol and poly-
The component of vinylamine for example is tended to form hydrogen bond.Accordingly, it is possible to the case where be, for producing the component of particulate composition in institute
Obtaining in final products is partially or completely modified form.The present invention also includes the component of this modification.
In a particularly preferred embodiment of the method, particulate composition of the invention includes:
(i) urea；
And the additive comprising component (ii) and component (iii):
(ii) combination of polyethyleneimine and polyvinyl alcohol or the combination of polyethyleneimine and polyvinylamine；
(iii) selected from aliphatic dicarboxylic acid, its salt and acid anhydrides, aliphatic tricarboxylic acids, its salt and acid anhydrides, aromatic dicarboxylic acid and acid anhydrides
At least one of compound；
Wherein it is preferred to which the ratio by mass of component (i) is calculated as > 97 weight % and described in the particulate composition
The ratio by mass of the summation of component (ii) and component (iii) is calculated as < 1 weight % in particulate composition.
If composition of the invention includes aliphatic dicarboxylic acid as component (iii), can be preferably chosen from: grass
Acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecane
Diacid, tridecandioic acid, tetracosandioic acid, hexadecandioic acid (hexadecane diacid) and respective acid anhydrides.It is highly preferred that existing component (iii)
Dicarboxylic acids be oxalic acid, succinic acid or both acid mixtures.
If composition of the invention includes aliphatic tricarboxylic acids as component (iii), lemon can be preferably chosen from
Acid, isocitric acid and respective acid anhydrides.The tricarboxylic acids of existing component (iii) is more preferably citric acid.
If composition of the invention includes aromatic dicarboxylic acid or its acid anhydrides as component (iii), can be preferably
Selected from phthalic acid, phthalic anhydride, M-phthalic acid and terephthalic acid (TPA).The aromatics dicarboxyl of existing component (iii)
Acid or its acid anhydrides are more preferably or mixtures thereof phthalic acid, phthalic anhydride.
In another preferred embodiment of the method, particulate composition includes:
(i) urea；
And the additive comprising component (ii) and component (iii):
(ii) combination of polyethyleneimine and polyvinylamine；
(iii) selected from least one of oxalic acid, succinic acid, citric acid, phthalic acid and phthalic anhydride chemical combination
Object；
Wherein the ratio by mass of component (i) is calculated as > 97 weight % in the particulate composition, in the particulate composition
The ratio by mass of the summation of component (ii) and component (iii) is calculated as < 1 weight %.
The particularly preferred embodiment of particulate composition in the method includes:
(i) urea；
And it is selected from the additive of group (a) to (g):
(a) comprising the combined additive of (ii) polyethyleneimine and polyvinylamine；
(c) additive of combination and (iii) oxalic acid comprising (ii) polyethyleneimine and polyvinylamine；
(d) additive of combination and (iii) citric acid comprising (ii) polyethyleneimine and polyvinylamine；
(e) additive of combination and (iii) succinic acid comprising (ii) polyethyleneimine and polyvinylamine；
(f) additive of combination and (iii) phthalic acid comprising (ii) polyethyleneimine and polyvinylamine；
(g) additive of combination and (iii) phthalic anhydride comprising (ii) polyethyleneimine and polyvinylamine；
Wherein the ratio by mass of component (i) is calculated as > 97 weight % in the particulate composition, in the particulate composition
The ratio by mass of the summation of component (ii) and component (iii) is calculated as < 1 weight %.
In the particulate composition ratio by mass of component (i) it is preferred > 97 weight %, more preferably > 98 weight %,
Most preferably > 98.5 weight %.
The ratio by weight of additive component can for example according to used component (ii) and component (iii) and
Variation.Preferably, the ratio by mass of the summation of component (ii) and component (iii) is calculated as < 0.5 weight in the particulate composition
Measure %, more preferably < 0.4 weight %, even more preferably < 0.3 weight %, or even further preferably < 0.25 weight %.
If additive component includes two or more components, relative scale can also change.For example, component
It (ii) can be in 1:20 to 20:1, preferably 1:15 to 15:1, more preferable 1:10 to 10:1 with the components by weight of component (iii)
In the range of, and including incremental value therebetween.
The particularly preferred embodiment of the particulate composition of the method includes the group of polyethyleneimine and polyvinylamine
It closes.The weight ratio of polyethyleneimine and polyvinylamine is alterable in the combination of both components, such as in 1:20 to 20:1, preferably
In the range of 1:15 to 15:1, more preferable 1:10 to 10:1, and including incremental value therebetween.
In addition, the combination of two kinds of component polyethyleneimines and polyvinylamine and the weight ratio of component (iii) can also change,
And it in each case, can be for example in 1:20 to 20:1, preferably 1:15 to 15:1, the range of more preferable 1:10 to 10:1
It is interior, and including incremental value therebetween.
In a preferred embodiment of the method, particulate composition of the invention is substantially free of formaldehyde.At this
In the context of invention, statement means that the composition includes < 0.1 weight %, preferably < 0.05 weight " substantially free of formaldehyde "
Measure the formaldehyde of %, more preferably < 0.005 weight %, even more preferably < 0.0005 weight %.
The invention also includes the NO that can be obtained by means of the present inventionx32 solution of reducing agent AUS is (at diesel exhaust gas
Manage liquid).The NOxThe impurity (being limited by particulate additive) of 32 solution of reducing agent AUS is different from urea solution in pure water.Especially
Ground, polymer additive except this method except through being difficult to characterize in any other manner.
All preferred embodiments for having combined particulate composition of the invention to describe above also correspondingly apply to add
Agent is used to produce the purposes of the present invention of the particulate composition comprising urea, therefore is not repeated here.
For sake of completeness, following discloses be used to produce the particle comprising urea according to WO 2015/193377A1
The alternatively possible method of composition comprising following steps:
(A) it provides and contains urea solution；
(B) it in the case where addition has the additive formed as described above, pelletizes to containing urea solution.
It is public that all preferred embodiments for having combined particulate composition of the invention to describe above also correspondingly apply to institute
The method for producing the particulate composition comprising urea opened, therefore be not repeated here.
In a preferred embodiment of the method for producing particulate composition, solution used in step (A)
Urea content > 60 weight %, preferably > 95 weight %, more preferably > 97 weight %, even more preferably > 98 weight %, or even further preferably >
98.5 weight %.
In step (B), adding the additivated granulation containing urea solution can be by well known by persons skilled in the art normal
Rule method carries out, such as by means of spray crystallization (granulation), rotary drum granulation or fluidized bed granulation.
In one of the method for producing particulate composition open embodiment, in step (B) granulation by means of
Fluidized bed granulation carries out comprising following steps:
(B1) seed crystal containing urea is provided；
(B2) seed crystal containing urea is fluidized；
(B3) using, there is the additive formed as described above will contain urea solution applies by spraying.
If additive includes two or more components, these can respectively be used alone in the method for the invention
Or it is used together, or used in the form of premix.The opportunity of component and addition can change.For example, can will be a kind of
Or more component be added to provided by urea solution, or only before it faces spraying application by one or more of components
It is added to containing in urea solution.According to the characteristic of component, it can be advantageous that come in the form of solution, suspended substance, lotion etc. using group
Point.Suitable liquid for solution or other preparations particularly includes water, but also includes organic solvent, such as alcohol, ether etc..
Temperature containing urea solution is preferred > and 130 DEG C.
In an embodiment for producing particulate composition, the method includes the steps (C):
(C) three kinds of fractions are divided into after producing particle urea compositions, wherein
A kind of fraction (F1) includes the particle with expectation target size,
A kind of fraction (F2) is greater than the particle of expectation target size comprising size, and
A kind of fraction (F3) is less than the particle of expectation target size comprising size, and
Wherein it is preferred to which fraction F2 is recycled back into this method after particle crushing, and fraction F3 is followed again
It is looped back in this method.
For producing urea and for being further processed in the equipment to generate particulate composition, usually also obtain
Ammonia.This can be converted to corresponding ammonium salt by washing operation with suitable sour (such as nitric acid or sulfuric acid), for example, ammonium nitrate or
Ammonium sulfate, and these can be conveyed to further use, such as be used in fertilizer.Appropriate method and step for pickling
Suddenly it is described in such as WO 2010/060535.
In another embodiment for producing particulate composition, disclosed method includes step (D):
(D) pickling.
The acid of said components (iii) can also be advantageously used to carry out in pickling.
Another disclosed aspect of the invention is related to the equipment for producing the particulate composition comprising urea comprising:
(a) granulator；
(b) at least one device for being used to add additive as described above；
(c) at least one device for being used to for the particulate composition being divided into varying particle size fraction；
(d) optionally at least one for carrying out the device of pickling.
In a preferred embodiment of present device, granulator (a) is fluidised bed granulator.
Disclosed equipment is especially suitable for carrying out disclosed method.
Another aspect of the present invention relates to the purposes of 32 solution of AUS of urea in the water obtained according to the present invention in the following:
Diesel-engine road vehicle, furnace, waste incinerator, gas turbine, engine of boat and ship or the industrial equipment for nitrogen oxides reduction.For
This, by the solution injection such as exhaust stream from vehicle of the invention, and makes nitrogen oxides in SCR catalyst (such as by titanium
Constitute) on be reduced to N2And H2O.The mechanism for example at isocyanic acid and then hydrolyzes ammonification and carries out by being pyrolyzed urea.Ammonia is most
Eventually on a catalyst with reaction of nitrogen oxides.
The present invention is illustrated by the following examples.These elaborations are merely illustrative, and are not intended to limit general model of the invention
It encloses.
Embodiment:
Embodiment 1
In testing equipment, about 108 DEG C at a temperature of, in the fluidized bed system of the cylindrical fluid bed with diameter 40cm
It pelletizes in grain machine to urea.Fluidized bed is terminated in its lower end by the perforated plate that bore dia is 2.0mm.Make fluidization air with about
2m/ seconds apparent velocities flow into fluidized bed.In the side-walls of bed overflow is installed above substrate at 10cm.Then it will determine and measure
The urea particle with narrow size distribution or urea granula of (about 45kg) are introduced into granulation column as the seed crystal for pelletizing.It will tool
There is the bed (about 50cm is deep) of seed crystal to be fluidized with the hot-air that temperature is about 100 DEG C, is envisaged for running once bed has reached
About 108 DEG C of temperature, begin to addition about 135 DEG C temperature 96 weight % to 97 weight % urea solution.Then pass through
The urea solution that water content is 3 weight % to 4 weight % is introduced fluidized bed from holding vessel with 350kg/ hours rates by nozzle
In granulator, the nozzle about 140 DEG C at a temperature of operate, supply air with 240kg/ hours rates.Then by root
It is mixed under about 135 ° with urea solution according to the additive for granulation that the following table 1 uses.With 5 minutes regular intervals via outlet
Solid is discharged, from fluidized bed to realize the substantially invariable height of bed.Then the solid sample thus removed is respectively sieved
To be really sized distribution.There is no solid to be recycled in fluidised bed granulator.The duration of every batch of is in each case
About 30 minutes.After this period, stops charging, bulk material is cooled to about 100 DEG C and is moved from fluidised bed granulator
Out, and by being sieved into different fractions it is separated.Then it will be cooled to about with the fraction that desired size is distributed
60 DEG C to analyze its product property.All fractions are carried out with the growth rate for being weighed to determine bulk material.In addition, also collecting
It weighs from the dust of the bag filter of exhaust device and to it.
According to above-mentioned steps, is not also adding additive and there is polyvinylamine (PVA), polyvinylamine/polyethyleneimine
The comparative test pelletized in the case where amine blends or standard additive (urea-formaldehyde additive UF80), and to every kind
In the case of the bulk material that obtains correspondingly post-processed and analyzed.
The following table 1 a shows the corresponding assessment of the bulk material for dust formation, compression strength, density and agglomeration.Equally
The sensibility that the dust of explanation is formed is the result to the visual assessment for the dust collected by small-sized fluidized bed cooler.For commenting
Estimate in the grade b shown in table 1 of bulk material obtained.
Table 1a
PVA: polyvinylamine PEI: polyethyleneimine
1) mixture in each case based on PVA and PEI
2) mixture based on PVA, PEI and oxalic acid in each case
Table 1b
Embodiment 2
According to step described in embodiment 1, to by various dose oxalic acid and 500mg/kg polyethyleneimine and poly- second
The mixture (in each case, the mixture based on polyethyleneimine and polyvinylamine, the 40 weight % of weight %/60) of enamine
The effect of the granule additive of the invention constituted is measured.This storage by the way that oxalic acid to be introduced into urea solution before the spraying
It deposits in tank and polyethyleneimine/polyvinylamine mixture is fed to supply into the urea stream of nozzle to carry out.Then 132
The urea solution that thus obtained water content is 3 weight % is supplied with 350kg/ hours rates at a temperature of DEG C, and such as embodiment 1
Described in post-processed.It is carried out similarly accordingly with the comparative test of formaldehyde.
The following table 2 shows the respective ratio of dust in fluidised bed granulator:
Table 2:
To the bulk material obtained according to embodiment 1 to 2 studies have shown that when adding additive of the invention, dust
It is formed and the characteristic (compression strength, caking tendency) of bulk material is improved.The knot obtained when the result is with using formaldehyde
Fruit is suitable or even better, and needs significant lesser amount of additive.
Embodiment 3:
Embodiment 3 has been shown in table 3 the comparison urea of the urea (the typical urea for being used as fertilizer) with typical fertilizer grade
Solution is compared between urea solution of the invention.
Table 3
From table 3 it is observed that with 32.5 weight % ureas urea solution of the invention meet specification (DIN 70070:
The table 1 of 2005-08) in the limitation that provides.In the typical commercial urea solution (fertilizer grade urea) equally with 32.5 weight % ureas
In the case of, the value of aldehyde is much higher than limitation.The content of biuret is in restricted area.In typical business urea solution (fertilizer grade urea)
Other ratios do not specify (n.s.).
The very high aldehyde as known to comparable typical commercial urea solution, is equally exploited for fertilizer field
Possibility purposes of the particle urea compositions of the invention in 32 solution of AUS (diesel exhaust fluid) field be to exceed to anticipate
Material.Meanwhile compared with the urea of technical grade purity, particulate composition of the invention preferably can be dried and be transported.This hair
Bright particulate composition shows that granule stability more higher than pure technical grade urea, storability (agglomerate in technical grade urea
Be inclined to it is higher), lower dust formed and lower water imbibition.These disadvantages mentioned above make it difficult to by technical grade urea reproducibly
It prepares 32 solution of AUS (diesel exhaust fluid).
Claims (10)
1. one kind is for producing NOxThe method of 32 solution of reducing agent AUS (diesel exhaust fluid), including at least by water and
Grain composition mixing, the particulate composition includes:
(i) urea；
With the additive comprising component (ii):
(ii) combination of the amino-containing polymer of at least one packet or oligomer and at least one functional polyethylene based compound；
Wherein the ratio by mass of component (i) is calculated as > 60 weight %, component in the particulate composition in the particulate composition
(ii) ratio by mass is calculated as < 1 weight %, and
Urea solution is wherein obtained, and the ratio by mass of component (i) is not less than 31 weights in the urea solution obtained
It measures % and is not more than 34 weight %.
2. according to the method described in claim 1, wherein the additive includes component (iii):
(iii) change selected from aliphatic dicarboxylic acid and acid anhydrides, aliphatic at least one of tricarboxylic acids and acid anhydrides, aromatic dicarboxylic acid and acid anhydrides
Object is closed,
Wherein the ratio by mass of component (i) is calculated as > 60 weight %, component in the particulate composition in the particulate composition
(ii) and the ratio by mass of the summation of component (iii) is calculated as < 1 weight %.
3. method according to claim 1 or 2, wherein the particulate composition includes:
(i) urea；
With the additive comprising component (ii) and component (iii):
(ii) combination of polyethyleneimine and polyvinyl alcohol or the combination of polyethyleneimine and polyvinylamine；
(iii) change selected from aliphatic dicarboxylic acid and acid anhydrides, aliphatic at least one of tricarboxylic acids and acid anhydrides, aromatic dicarboxylic acid and acid anhydrides
Close object；
Wherein the ratio by mass of component (i) is calculated as > 97 weight %, component in the particulate composition in the particulate composition
(ii) and the ratio by mass of the summation of component (iii) is calculated as < 1 weight %.
4. according to the method in any one of claims 1 to 3, wherein the particulate composition includes:
(i) urea；
With the additive comprising component (ii) and component (iii):
(ii) combination of polyethyleneimine and polyvinylamine；
(iii) at least one of oxalic acid, succinic acid, citric acid, phthalic acid, phthalic anhydride compound are selected from；
Wherein the ratio by mass of component (i) is calculated as > 97 weight %, component in the particulate composition in the particulate composition
(ii) and the ratio by mass of the summation of component (iii) is calculated as < 1 weight %.
5. method according to claim 1 to 4, the wherein molecule of the polyethyleneimine in component (ii)
Amount is in the range of 500Da to 2000000Da.
6. the method according to any one of claims 1 to 5, the wherein molecular weight of the polyvinylamine in component (ii)
In the range of 500Da to 1000000Da.
7. method according to any one of claim 1 to 6, wherein in the composition component (i) ratio by mass
It is calculated as > 98 weight %, preferably > 98.5 weight %.
8. method according to any one of claim 1 to 7 is characterized in that component (ii) and component in the composition
(iii) ratio by mass of summation is calculated as < 0.5 weight %, preferably < 0.4 weight %, more preferably < 0.3 weight %, and most
It is preferred that < 0.25 weight %.
9. the NO of urea in the water obtained according to claim 1 to any one of 8xThe purposes of 32 solution of reducing agent AUS in the following:
Diesel-engine road vehicle, furnace, waste incinerator, gas turbine, engine of boat and ship or the industrial equipment for nitrogen oxides reduction.
10. a kind of NOx32 solution of reducing agent AUS (diesel exhaust fluid), can be by according to claim 1 in 8
Described in any item methods obtain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411492901.7A CN119258781A (en) | 2016-07-15 | 2017-07-13 | Use of urea composition in producing diesel exhaust fluid (AUS 32) |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102016213012 | 2016-07-15 | ||
| DE102016213012.9 | 2016-07-15 | ||
| PCT/EP2017/067657 WO2018011327A1 (en) | 2016-07-15 | 2017-07-13 | Use of a urea composition to produce diesel exhaust fluid (aus 32) |
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|---|---|---|---|
| CN202411492901.7A Division CN119258781A (en) | 2016-07-15 | 2017-07-13 | Use of urea composition in producing diesel exhaust fluid (AUS 32) |
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| CN109475814A true CN109475814A (en) | 2019-03-15 |
Family
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| CN202411492901.7A Pending CN119258781A (en) | 2016-07-15 | 2017-07-13 | Use of urea composition in producing diesel exhaust fluid (AUS 32) |
| CN201780043369.2A Pending CN109475814A (en) | 2016-07-15 | 2017-07-13 | Use of urea composition to produce diesel exhaust fluid (AUS 32) |
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| CN202411492901.7A Pending CN119258781A (en) | 2016-07-15 | 2017-07-13 | Use of urea composition in producing diesel exhaust fluid (AUS 32) |
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| US (1) | US20190292064A1 (en) |
| EP (1) | EP3484601B1 (en) |
| JP (1) | JP6802897B2 (en) |
| KR (1) | KR102181259B1 (en) |
| CN (2) | CN119258781A (en) |
| AR (1) | AR109052A1 (en) |
| AU (1) | AU2017297784B2 (en) |
| CA (1) | CA3028550C (en) |
| EA (1) | EA038075B1 (en) |
| ES (1) | ES2805071T3 (en) |
| LT (1) | LT3484601T (en) |
| PL (1) | PL3484601T3 (en) |
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| WO (1) | WO2018011327A1 (en) |
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| US12286391B2 (en) | 2020-10-09 | 2025-04-29 | AWA Technology LLC | Diesel exhaust fluid on demand system, apparatus, and method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102806011A (en) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | Method for preparing automobile urea liquid reducing agent |
| WO2015193377A1 (en) * | 2014-06-20 | 2015-12-23 | Uhde Fertilizer Technology B.V. | Urea composition and method for producing same |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1101641A (en) * | 1977-06-09 | 1981-05-26 | Anton Niks | Urea granulation |
| GB1581761A (en) | 1977-06-09 | 1980-12-17 | Azote Sa Cie Neerlandaise | Urea granulation |
| JPS62193631A (en) * | 1986-02-20 | 1987-08-25 | Nitto Electric Ind Co Ltd | Nitrogen oxide removing agent and nitrogen oxide removing body using said agent |
| US5766302A (en) | 1993-05-07 | 1998-06-16 | Lefroy; Roderick David Bruce | Fertilizer coating process |
| US20030072698A1 (en) * | 2000-08-28 | 2003-04-17 | Macarthur Brian W. | Apparatus for removing contaminants in reactors |
| DE10342551B4 (en) * | 2003-09-15 | 2016-08-11 | Skw Stickstoffwerke Piesteritz Gmbh | A process for the preparation of dicyandiamide and 1,2,4-triazole as urea-based fertilizer granules containing nitrification inhibitors and use of sublimation inhibitors for 1,2,4-triazole |
| NO321761B1 (en) * | 2004-06-30 | 2006-07-03 | Yara Int Asa | Process for improving crushing strength and reducing dust formation and tendency to cook urea, particles, and use of carbohydrates and optionally polyvinyl compounds as additive to molten urea |
| EP1843992B1 (en) * | 2005-01-14 | 2013-08-14 | YARA International ASA | Urea composition having reduced compressibility, caking and dust formation, and process for its preparation |
| NL1028497C2 (en) * | 2005-03-09 | 2006-09-12 | Dsm Ip Assets Bv | Process for the preparation of a urea-containing aqueous stream. |
| EP2192099A1 (en) | 2008-11-28 | 2010-06-02 | Uhde Fertilizer Technology B.V. | Urea granulation process with an acidic scrubbing system and the subsequent integration of ammonium salt into urea granules |
| JP2016064991A (en) * | 2014-09-22 | 2016-04-28 | 東洋エンジニアリング株式会社 | Method for producing high-purity urea aqueous solution in urea production process |
| KR101544503B1 (en) * | 2015-06-12 | 2015-08-21 | 경민워터컴(주) | Device for high purity ureasolution and manufacturing method thereof |
| DE102015122070A1 (en) * | 2015-12-17 | 2017-06-22 | Thyssenkrupp Ag | Urea-containing fertilizers and process for their preparation |
| CN105688669B (en) * | 2016-03-08 | 2018-03-09 | 江苏可兰素汽车环保科技有限公司 | Pectination polyacrylamide crystalloid increases agent interfering, the resistive connection crystal formation tail gas catalytic reducer prepared using the agent interfering and preparation method |
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2017
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- 2017-07-13 AU AU2017297784A patent/AU2017297784B2/en active Active
- 2017-07-13 ES ES17752006T patent/ES2805071T3/en active Active
- 2017-07-13 EA EA201990150A patent/EA038075B1/en not_active IP Right Cessation
- 2017-07-13 KR KR1020197001106A patent/KR102181259B1/en active Active
- 2017-07-13 CN CN202411492901.7A patent/CN119258781A/en active Pending
- 2017-07-13 CA CA3028550A patent/CA3028550C/en active Active
- 2017-07-13 CN CN201780043369.2A patent/CN109475814A/en active Pending
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- 2017-07-13 PL PL17752006T patent/PL3484601T3/en unknown
- 2017-07-13 US US16/317,277 patent/US20190292064A1/en not_active Abandoned
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102806011A (en) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | Method for preparing automobile urea liquid reducing agent |
| WO2015193377A1 (en) * | 2014-06-20 | 2015-12-23 | Uhde Fertilizer Technology B.V. | Urea composition and method for producing same |
Also Published As
| Publication number | Publication date |
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| EA201990150A1 (en) | 2019-05-31 |
| BR112019000792A2 (en) | 2019-04-24 |
| CN119258781A (en) | 2025-01-07 |
| EP3484601A1 (en) | 2019-05-22 |
| EP3484601B1 (en) | 2020-05-20 |
| SA519400904B1 (en) | 2022-04-03 |
| ES2805071T3 (en) | 2021-02-10 |
| AU2017297784A1 (en) | 2019-01-24 |
| EA038075B1 (en) | 2021-07-01 |
| CA3028550A1 (en) | 2018-01-18 |
| LT3484601T (en) | 2021-04-26 |
| JP6802897B2 (en) | 2020-12-23 |
| AU2017297784B2 (en) | 2020-02-20 |
| KR20190017972A (en) | 2019-02-20 |
| JP2019527683A (en) | 2019-10-03 |
| AR109052A1 (en) | 2018-10-24 |
| KR102181259B1 (en) | 2020-11-23 |
| CA3028550C (en) | 2021-06-15 |
| WO2018011327A1 (en) | 2018-01-18 |
| US20190292064A1 (en) | 2019-09-26 |
| PL3484601T3 (en) | 2020-11-16 |
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